WO2019177436A1 - 변성 중합 개시제 및 이의 제조방법 - Google Patents
변성 중합 개시제 및 이의 제조방법 Download PDFInfo
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- WO2019177436A1 WO2019177436A1 PCT/KR2019/003073 KR2019003073W WO2019177436A1 WO 2019177436 A1 WO2019177436 A1 WO 2019177436A1 KR 2019003073 W KR2019003073 W KR 2019003073W WO 2019177436 A1 WO2019177436 A1 WO 2019177436A1
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- WIPO (PCT)
- Prior art keywords
- carbon atoms
- formula
- group
- polymerization initiator
- compound represented
- Prior art date
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- 239000003505 polymerization initiator Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 127
- 239000000126 substance Substances 0.000 claims abstract description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 177
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000000376 reactant Substances 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- 125000000304 alkynyl group Chemical group 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 11
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 claims description 2
- CSBDTEMAXHVRBB-UHFFFAOYSA-N 2-ethoxy-n,n-dimethylethanamine Chemical compound CCOCCN(C)C CSBDTEMAXHVRBB-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 21
- 125000000524 functional group Chemical group 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 239000003999 initiator Substances 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 72
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 32
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 27
- 150000001993 dienes Chemical class 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- -1 styrene compound Chemical class 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 229920006978 SSBR Polymers 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000006138 lithiation reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- BOECHSSNNYQCRI-UHFFFAOYSA-N 2,3-dimethylbut-2-en-1-amine Chemical compound CC(C)=C(C)CN BOECHSSNNYQCRI-UHFFFAOYSA-N 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002900 organolithium compounds Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C*)=CCCC(*)(CN)C=C Chemical compound CC(C*)=CCCC(*)(CN)C=C 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Natural products CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical class C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical class C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 description 1
- 125000006747 (C2-C10) heterocycloalkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RRRXUCMQOPNVAT-UHFFFAOYSA-N 1-ethenyl-4-(4-methylphenyl)benzene Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=C)C=C1 RRRXUCMQOPNVAT-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
- C07C211/21—Monoamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
- C07C211/22—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton containing at least two amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/60—Polymerisation by the diene synthesis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
Definitions
- the present invention relates to a modified polymerization initiator capable of introducing a functional group into the polymer chain while simultaneously initiating a polymerization reaction and a method for preparing the same.
- a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
- As an evaluation index of the vulcanized rubber a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature or a small tan ⁇ Goodrich heat generation is preferable.
- the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding strength with the filler such as silica or carbon black. It is used a lot as a rubber material.
- SSBR solution polymerization SBR
- SSBR solution polymerization SBR
- fuel consumption can be reduced by appropriately adjusting the glass transition temperature.
- the SSBR is prepared using an anionic polymerization initiator, and the chain ends of the formed polymers are used by binding or modifying the chain ends of various polymers.
- an anionic polymerization initiator for example, US Pat. No. 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
- solution polymerization SSBR is prepared using an anionic polymerization initiator, wherein the anionic polymerization initiator is mainly used an organolithium compound.
- the organolithium compound is used as it is, or modified with a functional group-containing compound capable of imparting functional groups to the polymer chain.
- a method of preparing a modified polymerization initiator having a styrene-based structural unit, a conjugated diene-based structural unit or an arylamine structural unit by reacting a styrene compound, a conjugated diene-based compound, or an arylamine compound with an organolithium compound.
- JP3748277 describes an anionic polymerization initiator prepared by reacting an organolithium compound with an adduct in which the nitrogen of the cyclic second amine is bonded to the conjugated diene carbon, but the cyclic second amine remains when prepared by the reaction. In this reaction it can act as a scavenger (scavenger) and thus the yield of the anionic polymerization initiator can be lowered, and thus the process of filtration and purification after the reaction is essential. Therefore, there is a need for development of a modified polymerization initiator having excellent economic efficiency and good industrial applicability.
- the modified polymerization initiator used in the preparation of SSBR is widely used as a hexamethylene lithium initiator produced by the reaction of hexamethyleneimine (HMI) and n-butyllithium (BuLi) as shown in Scheme 1 below.
- HMI hexamethyleneimine
- BuLi n-butyllithium
- an anionic polymerization initiator such as a modified polymerization initiator is prepared through a batch process, or simultaneously produced an anionic polymerization initiator and SSBR in one batch reactor.
- the prepared anionic polymerization initiator inevitably requires a storage step before it is used to manufacture SSBR, and there occurs a problem of losing activity by reacting with various scavengers such as moisture and air during the storage time. As a result, it may adversely affect the post-processing and may act as a factor of deteriorating the physical properties of the finally produced SSBR.
- the anion polymerization initiator production reaction and the SSBR polymerization reaction are performed in the same batch reactor to solve the problem of storage, but it is difficult to confirm whether the synthesis of the anion polymerization initiator is properly performed, and the physical properties of the finally produced SSBR There is a problem that is worse than the case of adding a presynthesized anionic polymerization initiator.
- raw materials are directly introduced and mixed by reaction to produce by-products or reverse reactions to generate unreacted products, resulting in lower yields.
- Korean Unexamined Patent Publication No. 10-2016-0092227 discloses a method of preparing an anionic polymerization initiator using a continuous reactor including a static mixer.
- the concentration distribution and temperature distribution of the raw materials can be made uniform, and the lithiation reaction proceeds continuously, thereby reducing the storage problem and the yield reduction problem.
- the static mixer is used to solve the exothermic reaction problem of the lithiation reaction.
- the manufacturing cost is high because a special cooling device is not required.
- the present invention has been made in order to solve the problems of the prior art, and an object of the present invention is to provide a modified polymerization initiator that can be used in a polymerization reaction to easily initiate a reaction and can provide a filler affinity functional group to a polymer. do.
- an object of the present invention is to provide a method for producing a modified polymerization initiator capable of producing the modified polymerization initiator with a high conversion rate by minimizing side reactions.
- the present invention provides a modified polymerization initiator comprising at least one compound derived unit represented by the formula (1) and a compound derived unit represented by the formula (2):
- A is -NR a R b , -OR c , or -SR d ,
- R a to R d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, an aryl group having 3 to 30 carbon atoms, and carbon atoms
- M is an alkali metal
- R e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
- the present invention provides a method for preparing a modified polymerization initiator according to claim 1, comprising the step of reacting a compound represented by the formula (1) and a compound represented by the formula (2):
- A is -NR a R b , -OR c , or -SR d ,
- R a to R d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, an aryl group having 3 to 30 carbon atoms, and carbon atoms
- M is an alkali metal
- R e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
- the modified polymerization initiator according to the present invention may include various functional groups in the molecule by including the compound-derived unit represented by the formula (1), thereby initiating the polymerization reaction and introducing functional groups into the polymer chain.
- the production method according to the present invention can be easily used in the polymerization of the polymer to easily start the polymerization while at the same time can easily prepare a modified polymerization initiator capable of providing a filler affinity functional group to the polymer, in addition to the continuous reactor It can be carried out through a continuous reaction to reduce the generation of unreacted material in the lithiation reaction, and to reduce the production of by-products by reducing the problems caused by the exothermic reaction of the lithiation reaction with a rapid heat removal, thereby reducing the conversion rate It can be improved and a high purity modified polymerization initiator can be produced in high yield.
- the term 'substituted' may mean that the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent.
- the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, the functional group, the atomic group, Alternatively, one, two or more substituents may be present depending on the number of hydrogens present in the compound, and when a plurality of substituents are present, the substituents may be the same as or different from each other.
- alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl and sec-butyl. And branched alkyl groups such as tert-butyl and neo-pentyl may be included.
- 'alkylene group' used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, butylene, and the like.
- alkenyl group' used in the present invention may mean an alkyl group including one or two or more double bonds.
- alkynyl group' used in the present invention may refer to an alkyl group including one or two or more triple bonds.
- 'cycloalkyl group' used in the present invention may mean both cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.
- aryl group used in the present invention may mean a cyclic aromatic hydrocarbon, and also monocyclic aromatic hydrocarbon in which one ring is formed, or polycyclic aromatic hydrocarbon in which two or more rings are bonded ( polycyclic aromatic hydrocarbons) may include both.
- the terms 'derived unit' and 'derived functional group' may refer to components, structures, or the substance itself resulting from a substance.
- the present invention provides a modified polymerization initiator that can act as a polymerization initiator to initiate polymerization upon polymerization of a polymer, in particular a conjugated diene-based polymer, and at the same time act as a modifier to introduce functional groups into the polymer chain.
- the modified polymerization initiator according to an embodiment of the present invention is characterized by including a compound derived unit represented by Formula 1 and a compound derived unit represented by Formula 2 below.
- A is -NR a R b , -OR c , or -SR d ,
- R a to R d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, an aryl group having 3 to 30 carbon atoms, and carbon atoms
- M is an alkali metal
- R e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
- A is -NR a R b , -OR c , or -SR d , wherein R a to R d are independently from each other N, O, S, Si and F atoms It may be unsubstituted or substituted with a substituent including one or more selected heteroatoms, and when unsubstituted, R a to R d independently of each other, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and carbon atoms C2-C20 cycloalkyl group, C3-C20 cycloalkyl group, C6-C20 aryl group, C1-C20 heteroalkyl group, C2-C20 heteroalkenyl group, C2-C20 heteroalkynyl group, C2-C20 It may be a heterocycloalkyl group of 2 to 20 or a heteroaryl group of 3 to 20 carbon atoms.
- R a and R b are connected to each other to be substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aliphatic hydrocarbon ring group having 5 to 10 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or It may be to form a heterocyclic group having 3 to 10 carbon atoms, wherein the heterocyclic group wherein at least one of the carbon atoms forming the ring is substituted with a hetero atom, wherein the hetero atom is selected from N, O, S, Si and F atoms It may be one or more selected.
- A may be selected from substituents represented by Chemical Formulas 1a to 1c.
- R 1 , R 2 , R 5 , R 7 and R 8 are independently of each other an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon atoms 3-10 aryl group, C1-C10 heteroalkyl group, C2-C10 heteroalkenyl group, C2-C10 heteroalkynyl group, C2-C10 heterocycloalkyl group, or C3-C10 heteroaryl group
- R 1 and R 2 and R 7 and R 8 may be bonded to each other to form an aliphatic hydrocarbon ring group having 5 to 20 carbon atoms or an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, wherein R 1 and R 2 , R 5 , R 7 and R 8 are each unsubstituted or substituted with a substituent including one or more heteroatoms selected from N
- R 3 , R 4 and R 6 are each independently substituted with a substituent including an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or a hetero atom selected from N and O atoms or It is an unsubstituted alkylene group having 1 to 10 carbon atoms,
- X and Z are each independently selected from N, O and S atoms, and when X is O or S, R 8 is not present, and when Z is O or S, R 5 is not present.
- R 1 , R 2 , R 5 , R 7 and R 8 are independently substituted or unsubstituted with a substituent including one or more heteroatoms selected from N, O and S atoms.
- An alkyl group having 1 to 10 carbon atoms wherein R 1 and R 2 and R 7 and R 8 are each bonded to each other to form an aliphatic hydrocarbon ring group having 5 to 10 carbon atoms or an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, and R is 3 , R 4 and R 6 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, R 5 is an alkyl group having 1 to 10 carbon atoms, and X and Z are each independently It may be one selected from N, O and S atoms, R 8 is not present when X is O or S, R 5 may not be present when Z is O or S.
- the myrcene derivative compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-1 to Chemical Formula 1-11.
- M is an alkali metal
- R e is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. It may be an aryl group of 10 to 10, specifically, in the formula (2) M may be Na, K or Li, R e may be hydrogen or an alkyl group having 1 to 10 carbon atoms.
- modified polymerization initiator may be a single material or may be in the form of a mixture of several materials, where the mixture may mean that several isomers are present together.
- the modified polymerization initiator may be one containing at least one selected from the group consisting of a compound represented by the following formula (3) and isomers thereof.
- A is as defined in Formula 1, M is Na, K or Li, R e is hydrogen or an alkyl group having 1 to 10 carbon atoms.
- M may be bonded to an adjacent carbon by an ionic bond.
- the isomer of the compound represented by Formula 3 may include all of the structural isomers and stereoisomers of the compound represented by Formula 3, and for example, the compounds represented by Formulas 3-1 to 3-3. Can be.
- the modified polymerization initiator according to an embodiment of the present invention is to include one or more selected from dimers, trimers and oligomers of the compound represented by the formula (3) and isomers thereof. Can be.
- the dimer may represent a form in which two compound-derived units represented by Formula 1 and one compound-derived unit represented by Formula 2 are combined per molecule, and the trimer is a compound-derived unit represented by Formula 1 It may represent a form in which three and one derived unit represented by the formula (2) is bonded, the oligomer may represent a form in which a plurality of compound derived units represented by the formula (1) and one derived unit represented by the formula (2) are combined. have.
- the compound represented by Chemical Formula 1 may be prepared by reacting a functional group compound with mircene (myrcene), for example, the following Method 1 and Method according to the substituent A in Chemical Formula 1 It may be prepared by one or more of the two methods of two.
- mircene myrcene
- the compound represented by Chemical Formula 1 is prepared by reacting a compound represented by Chemical Formula 4 with an alkylsulfonyl chloride-based compound in the presence of an organic solvent, thereby preparing a compound represented by Chemical Formula 5. ; It may be prepared through the step of reacting the compound represented by the formula (5) and the compound represented by the formula (6).
- A is as defined above, D is a living group (leaving group).
- the compound represented by Chemical Formula 4 may be prepared by, for example, a reaction as in Scheme 3 below.
- the compound represented by Chemical Formula 1 is prepared by reacting a compound represented by Chemical Formula 6 with an alkylsulfonyl chloride-based compound in the presence of an organic solvent to produce a compound represented by Chemical Formula 7. step; And reacting the compound represented by Formula 7 with the compound represented by Formula 4 below.
- this invention provides the manufacturing method of said modified polymerization initiator.
- Method for producing the modified polymerization initiator according to an embodiment of the present invention is characterized in that it comprises the step of reacting the compound represented by the formula (1) and the compound represented by the formula (2).
- the compound represented by Formula 1 and the compound represented by Formula 2 may be reacted in a molar ratio of 1: 0.5 to 5.0, the reaction is a temperature range of 0 °C to 80 °C and It may be performed under a pressure condition of 0.5 bar to 10 bar.
- the reaction may be carried out via a batch or continuous reaction, wherein the batch reaction and the continuous reaction may be carried out under the same conditions except for the reaction form, Therefore, it may be carried out under different conditions so as to be more suitable according to each reaction type.
- the compound represented by Formula 1 and the compound represented by Formula 2 may be reacted in a molar ratio of 1: 0.5 to 3.0, more specifically 1: 1 It may be reacted at a molar ratio of 2 to 2.
- reaction of the compound represented by Formula 1 and the compound represented by Formula 2 may be carried out at a temperature range of 0 °C to 45 °C and pressure conditions above atmospheric pressure, specifically, the temperature range of 20 °C to 30 °C And it may be performed at a pressure condition of 0.5 bar to 2 bar.
- the reaction may be carried out in the presence of a polar additive in order to control the reactivity of the compound represented by the formula (1) and the compound represented by the formula (2), wherein the polar additive is not particularly limited, for example tetrahydrofuran, ditetra Hydrofuryl propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene diethyl ether, diethyl glycol, dimethyl glycol, tert-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (Dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine may be included at least one selected from the group consisting of.
- the polar additive may be used in a molar ratio of 1.0 to 5.0 with respect to 1 mole of the compound represented by Formula 1.
- the reaction when the reaction is carried out through a continuous reaction, the reaction is carried out in a continuous reactor comprising a first continuous channel and a second continuous channel, before the reaction ,
- the first reactant comprising the compound represented by formula 1 is introduced into the continuous reactor through the first continuous channel
- the second reactant comprising the compound represented by formula 2 is continuous through the second continuous channel It may be to be added to the reactor.
- the reaction may be performed in a continuous reactor.
- the continuous reactor may represent a reactor that advances the reaction while continuously inputting the raw material used for the reaction.
- the reaction may be performed in a continuous reactor including a first continuous channel and a second continuous channel, the first reactant comprising the compound represented by the formula (1) before the reaction is the first continuous
- the second reactant which is introduced into the continuous reactor through the food channel and includes the compound represented by Formula 2, may be introduced into the continuous reactor through the second continuous channel.
- the first continuous channel and the second continuous channel may respectively mean an input unit (or injection unit) for adjusting the input amount of each of the first reactant and the second reactant in the continuous reactor,
- the input amount of the first reactant and the second reactant may be adjusted independently of each other, and through this, the input amount may be adjusted according to the reaction environment, thereby minimizing side reactions.
- reaction may be carried out under a temperature range of 0 °C to 80 °C, or 15 °C to 50 °C and pressure conditions of 0.5 bar to 10 bar, or 1 bar to 4 bar, the reaction rate is within this range It is excellent and has the effect of minimizing side reactions.
- the first reactant may be introduced into the continuous reactor at a rate of 1.0 g / min to 20.0 g / min through the first continuous channel, and the second reactant is 1.0 g / min through the second continuous channel.
- min to 20.0 g / min may be introduced into the continuous reactor.
- the first reactant may be introduced into the continuous reactor at a rate of 1.5 g / min to 8.5 g / min through the first continuous channel, and the second reactant is 1.5 through the second continuous channel. It may be introduced into the continuous reactor at a rate of g / min to 8.5 g / min, within this range to minimize side reactions by appropriately adjusted without sudden changes in the dosage of the compound represented by the formula (1) and the compound represented by the formula (2) can do.
- the compound represented by Formula 1 and the compound represented by Formula 2 may be reacted in a molar ratio of 1: 0.5 to 1: 5, specifically, the compound represented by Formula 1 and represented by Formula 2 The compound may be reacted in a molar ratio of 1: 0.8 to 1: 1.5.
- side reactions may be reduced.
- the first reactant may be a material having a fluidity so that the compound represented by the formula (1) is easily introduced into the continuous reactor to participate in the reaction, for example, the first reactant is the compound represented by the formula (1), Or it may be a solution containing a compound represented by the formula (1) and a reaction solvent.
- the second reactant may be a material having fluidity such that the compound represented by Chemical Formula 2 may be easily introduced into the continuous reactor to participate in the reaction.
- the second reactant may be the compound represented by Chemical Formula 2, or Or it may be a solution containing a compound represented by the formula (2) and a reaction solvent.
- the concentration of the solution is not particularly limited, and the compound represented by Formula 1 and the compound represented by Formula 2 may be adjusted to have the aforementioned molar ratio.
- the reaction solvent may be a hydrocarbon solvent that does not react with anions, such as linear hydrocarbon compounds such as pentane, hexane and octane; Derivatives thereof having a side branch; Cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; Aromatic hydrocarbon compounds such as benzene, toluene and xylene; And linear and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran.
- the reaction solvent may be cyclohexane, hexane, tetrahydrofuran or diethyl ether.
- the reaction according to an embodiment of the present invention can be carried out in the presence of a polar additive, if necessary, wherein the polar additive is included in the first reactant, or is included in the second reactant is introduced into the continuous reactor
- the polar additive may be included in the first reactant and introduced into the continuous reactor.
- the first reactant may include a polar additive, in which case the polar additive may be included in the first reactant in a molar ratio of 1.0 to 5.0 with respect to 1 mole of the compound represented by Formula 1, and this range Reactivity of the compound represented by the formula (1) and the compound represented by the formula (2) within the reaction can be easily adjusted to reduce the side reactions.
- the polar additive may be as described above.
- the yield may be better than the preparation method through a batch reaction.
- the reaction rate of the reaction raw materials may be increased during the lithiation reaction, thereby reducing the occurrence of unreacted materials.
- the production of by-products can be reduced by reducing the problems caused by the exothermic reaction of lithiation.
- the conversion rate can be improved to stably produce a high purity modified polymerization initiator in high yield.
- reproducibility may be superior to that of a batch reaction by continuously adding a reaction raw material and continuously performing a reaction, thereby preparing a modified polymerization initiator having a constant performance.
- the present invention provides a modified conjugated diene-based polymer comprising the functional group derived from the modified polymerization initiator.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may include a conjugated diene-based monomer-derived repeating unit, and may include a functional group derived from the modified polymerization initiator at at least one end thereof.
- the conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed by the conjugated diene-based monomer upon polymerization
- the conjugated diene-based monomer may be, for example, 1,3-butadiene, 2,3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) It may be at least one selected from the group.
- the modified conjugated diene-based polymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the conjugated diene-based monomer-derived repeating unit, and the aromatic vinyl monomer-derived repeating unit may be an aromatic vinyl-based
- the monomer may mean a repeating unit formed during polymerization, wherein the aromatic vinyl monomer may be, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methylstyrene, 4-propylstyrene, It may be at least one selected from the group consisting of 1-vinyl naphthalene, 4-cyclohexyl styrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H.
- GC / MS analysis uses ZB-5MS (0.25 mm (ID) ⁇ 30 ml, 0.25 ⁇ m df capillary) as a column, the gas flow (He) is 1 ml / min, oven temperature After 3 minutes at the initial 50 °C to 10 °C / min to 320 °C and maintained for 15 minutes, the injector temperature was measured by adjusting the 250 °C, split ratio 1/20, the injection amount 0.2 ⁇ l. In addition, the modified polymerization initiator was measured after protonation of the organolithium portion by quenching.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- Two vacuum dried 2L stainless steel pressure vessels were prepared. 1609 g of hexane, 1465 g of a compound represented by Chemical Formula 1-5, and 103 g of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 280 g of liquid 2.5M n-butyllithium (in hexane) and 1580 g of hexane were added to a second pressure vessel to prepare a second reactant. In this case, the molar ratio of the compound represented by the formula (1-5), n-butyllithium and tetramethylethylenediamine was 1: 1: 1.4.
- the mass flow meter was used to draw the first reactant into the first continuous channel at a feed rate of 1.0 g / min and to the second continuous channel in a continuous reactor. Two reactants were each injected at an injection rate of 1.0 g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 °C, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula Was prepared.
- backpressure regulator backpressure regulator
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- Two vacuum dried 2L stainless steel pressure vessels were prepared. 1609 g of hexane, 1484 g of a compound represented by Chemical Formula 1-7, and 103 g of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 280 g of liquid 2.5M n-butyllithium (in hexane) and 1580 g of hexane were added to a second pressure vessel to prepare a second reactant. At this time, the molar ratio of the compound represented by the formula (1-7), n-butyllithium and tetramethylethylenediamine was 1: 1: 1.4.
- the mass flow meter was used to draw the first reactant into the first continuous channel at a feed rate of 1.0 g / min and to the second continuous channel in a continuous reactor. Two reactants were each injected at an injection rate of 1.0 g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 °C, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula (ii) Was prepared.
- backpressure regulator backpressure regulator
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- Two vacuum dried 2L stainless steel pressure vessels were prepared. 1609 g of hexane, 1383 g of a compound represented by Chemical Formula 1-6, and 103 g of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 280 g of liquid 2.5M n-butyllithium (in hexane) and 1580 g of hexane were added to a second pressure vessel to prepare a second reactant. At this time, the molar ratio of the compound represented by the formula (1-6), n-butyllithium and tetramethylethylenediamine was 1: 1: 1.4.
- the mass flow meter was used to draw the first reactant into the first continuous channel at a feed rate of 1.0 g / min and to the second continuous channel in a continuous reactor. Two reactants were each injected at an injection rate of 1.0 g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 °C, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula (iii) Was prepared.
- backpressure regulator backpressure regulator
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- Two vacuum dried 2L stainless steel pressure vessels were prepared. 1609 g of hexane, 1121 g of a compound represented by Chemical Formula 1-1, and 103 g of tetramethylethylenediamine were added to a first pressure vessel, thereby preparing a first reactant. At the same time, 280 g of liquid 2.5M n-butyllithium (in hexane) and 1580 g of hexane were added to a second pressure vessel to prepare a second reactant. At this time, the molar ratio of the compound represented by the formula (1-1), n-butyllithium and tetramethylethylenediamine was 1: 1: 1.4.
- the mass flow meter was used to draw the first reactant into the first continuous channel at a feed rate of 1.0 g / min and to the second continuous channel in a continuous reactor. Two reactants were each injected at an injection rate of 1.0 g / min. Subsequently, the temperature of the continuous reactor is maintained at 25 ° C., and the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator.
- the modified polymerization initiator including the compound represented by the following Formula iv Was prepared.
- the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.
- Modified conjugated diene-based polymers comprising functional groups derived from the modified polymerization initiator were prepared using the modified polymerization initiators prepared in Examples 1 to 9.
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water to prepare a modified styrene-butadiene copolymer. Elemental analysis of each of the prepared copolymers confirmed that nitrogen atoms exist in the copolymer chain.
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EP19767697.6A EP3636652B1 (en) | 2018-03-16 | 2019-03-15 | Modified polymerization initiator and preparation method therefor |
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